Viscose solution



United Statfi o VISCOSE SOLUTION Byron A. Thurnrn, Swarthmore, Pa., assignor to Ameri-.

, can Viscose Corporation, Philadelphia, Pa., a corporation of Delaware 2 Claims, Cl. 106-165) This invention relates to the productionof shaped bodies of regenerated cellulose from viscose and more particularly to filaments and fibers of regenerated cellulose from viscose.

In the conventional methods of producing shaped bodies of regenerated cellulose from viscose, a suitable cellulosic material such as purified cotton linters, wood pulp, mixtures thereof, and the like is first converted to an alkali cellulose by treatment with a caustic soda solution and after shredding the. treated cellulose material, it is allowed to'age. Theaged alkali cellulose is then converted tov a xanthate by treatment with carbon disulfide. The cellulose xanthate is subsequently dissolved in a caustic soda solution in an amount calculated to provide a viscose of the desired cellulose and alkali content. 'After filtration, the viscose solution is allowed to ripen and is subsequently extruded through a shaped orifice into a suitable coagulating and regenerating bath.

In the production of shaped bodies such as filaments, the viscose solution is extruded through a spinneret into a coagulating and regenerating bath consisting of an aqueous acid solution containing zinc sulfate. The filament may subsequently be passed through a hot aqueous bath where it is stretched to improve its properties such as tensile strength. 'The filament may; then be passed through a dilute aqueous solution of sulfuric'acid and sodium sulfate to complete the regeneration of the cellulose, in case it is not completely regenerated upon leaving the stretching stage. Thefilament is subsequently subjected to washing, purification, bleaching, possibly other"treating operations and' drying, being collected either'befor'e or after these treatments.

The filaments as formed by the conventional methods consist of a skin or outer shell portion and a core portion with a sharp line ofdemarkation between the two. The cross-section of the filaments exhibits a very irregular or crenulated exterior surface when even small amounts of zinc salts for certain other polyvalent metal salts are present in the spinning bath. The skin and core portions of the filament represent diiferences in structure and these diiferentportions possess different swelling and staining characteristics, the latter permitting a ready identification of skin and core. The sharply irregular and crenulated surface structure has a relatively low abrasion resistance and 'readily picks up foreign particles such as dirt. Although the" core portion possesses a relatively hightensile strength, ithas a lowabrasion resistance and a low flex-life, is subject to fibrillation and is relatively stiff.

It has-now been discovered that the presence of small amounts of water-soluble alkylene 'oxide adducts of aniline in viscose, in the spinning bath, or in both the viscoseand the bath resultsin the production of shaped.

bodies of regenerated cellulose suchas filaments, films,

sheets and the like composed of all skin and having im-' proved properties and characteristics providing that the amount of the adduct is maintained with certain limits -Patented Feb. 2, 1960 2 and the composition of the spinning bath is maintained within certain composition limits which will be defined hereinafter. The most readily distinguishable characteristics as compared to conventional filaments include a smooth, non-crenulated surface and the filaments consist entirelyof skin.

This invention contemplates the use of alkylene oxide adducts of aniline having from about 2 to about 50 or more alkylene oxide groups per molecule, preferably from about 4 to about 30 alkylene oxide units per molecule of aniline. It is obvious that for all practical purposes considering cost, ease of preparation, commercial availabilityand solubility in water, in alkali solutions and in acid solutions, the ethylene oxide adductsare preferred. Theoretically, an alkylene oxide adduct such as ethylene oxide adduct of aniline containing 4 ethylene oxide units per molecule of aniline would consist of a compound in which each of the amino hydrogen atoms has been replaced with a chain of two ethylene oxide units. It is not necessary, however, that all of the amino hydrogens be replaced nor is it necessary that the ethylene oxide chains-replacing the difierent hydrogenatoms be the same in each'instance.

The term adduct is used herein to simplify the disclosure and description and designates a water-soluble N-substitlited aniline formed by the reaction between an alkylene oxide andaniline wherein the alkylene oxide or a polyoxyalkylene chain replaces one or both of the hydrogen atoms attached'to the nitrogen atom. It is not necessary to' employ individual specific compounds of the type described and the reaction. products which probably consist of mixture of specific compounds, the average alkylene oxide content per molecule of aniline being within the stated ranges, are satisfactory. Where, for example, each of the amino hydrogen atoms has been replaced with an alkylene oxide group, the compound is a N,N-di(beta-hydroxyalkyl)aniline. the amino hydrogen atoms has been replaced with a polyalkylene glycol radical, the compound is a N-mono- (omega-hydroxy polyoxyalkylene) aniline. Compounds in which both amino hydrogen atoms have been replaced withalkylene oxide chains are N,N-di(omega-hydroxy polyoxyalkylene) anilines.

The production of all skin products requires that certainminimum amounts of the alkylene oxide adduct be in solution in the viscose or in the spinning bath. Therefore, the alkylene oxide adduct must have sufficient solubility topermit the minimum amount of the adduct to be dissolved in the viscose or the spinning bath or both. The adduct may be conveniently added to the viscose in the form of a' solution in alkali or water and to the spinning bath in a solution of water or of the spinning bath.

Where the alkylene oxide adduct of aniline is to be added to the viscose, the amount of the adduct which is incorporated in viscose must be at least about 0.2% by weight of the cellulose in the viscose and may vary up to about 4%, preferably, the amount varies from 0.5% to 2%. Lesser amounts do not result in the production of products consisting entirely of skin and greater amountsafiectadversely the physical properties of the products. Amou nts'within the preferred range are most effective in enhancing the characteristics and properties of the products. The adduct of aniline may be added at any desired stage. in the production of the viscose such.

it is bein g dissolved in the caustic solution or to'the viscosesolution'before; or afterfiltration. [Ihe adduct is preferably added after the cellulose xanthate has been Where one of I dissolved in the caustic solution and prior to filtration.

The viscose may contain fromabout 6% to about 8% cellulose, the particular source of the cellulose being selected for the ultimate use of the regenerated cellulose product. The caustic soda content may be from about 4% to about 8% and the.carbon,disulfide content may be from about 30% to about 50% based upon the weight of the cellulose. The modified viscose, that is, a viscose containing the small amount of adduct, may have a salt test above about 7 and preferably above about 9 at the time of spinning or extrusion.

In order to obtain the improvements enumerated hereinbefore, it is essential that the composition of the spinning bath be maintained within a well defined range. The presence of the alkylene oxide adducts of aniline in the viscose or in the spinning bath combined with these limited spinning baths results in the production of yarns of improved properties such as high tenacity, high abrasion resistance, high fatigue resistance and consisting of filaments composed entirely of skin.

Generically and in terms of the industrial art, the spinning bath is a low acid-high zinc spinning bath. The bath should contain from about 10% to about 25% sodium sulfate and from about 3% to about 15% zinc sulfate, preferably from 15% to 22% sodium sulfate and from 4% to 9% zinc sulfate. Other metal sulfates such as iron, manganese, nickel and the like may be present and may replace some of the zinc sulfate. The temperature of the spinning bath may vary from about 25 C. to about 80 C., preferably between about 45 C. and about 70 C. In the production of the all skin type filaments, the temperature of the spinning bath is not critical, however, as is well known in the conventional practice in the art, certain of the physical properties such as tensile strength vary directly with the temperature of the spinning bath. Thus, in the production of filaments for tire cord purposes in accordance with the method of this invention, the spinning bath is preferably maintained at a temperature between about 55 C. and 65 C. so as to obtain the desired high tensile strength.

The acid content of the spinning bath is balanced against the composition of the viscose. The lower limit of the acid concentration, as is well known in the art, is just above the slubbing point, that is, the concentration at which small slubs of uncoagulated viscose appears in the strand as 'it leaves the spinning bath. For commercial operations, the acid concentration of the spinning bath is generally maintained about 0.4% to 0.5% above the slubbing point. For any specific viscose composition, the acid concentration of the spinning bath must be maintained above the slubbing point and below the point at which the neutralization of the caustic of the viscose is sufiiciently rapid to form a filament having a skin and core.

There is a maximum acid concentration for any specific viscose composition beyond which the neutralization is sufficiently rapid to produce filaments having a skin and core. For example, in general, the acid concentration of the spinning baths which are satisfactory for the production of the all skin products from a 7% cellulose, 6% caustic-viscose and containing the adducts of aniline lies between about and about 7.8%. The acid concentration may be increased as the amount of adduct is increased and also as the salt test of the viscose is increased. There is an upper limit, however, for the acid concentration based upon the amount of modifier and. the concentration of caustic in the viscose. All skin products cannot be obtained if the acid concentration is increased above the maximum value although the amount of the adduct of aniline is increased beyond about 4%, basedon the weight of the cellulose in the viscose, while other conditions are maintained constant. Increasing thecaustic soda content of the viscose beyond about 8% is uneconomical for commercial production methods. For example, a viscose containing about 7% in the art.

,4 cellulose, about 6% caustic soda, about 41% carbon disulfide, based on the weight of the cellulose, 1%, based on the weight of the cellulose, of an ethylene oxide adduct of aniline containing about 6 ethylene oxide units per molecule and having a salt test of about 10 when extruded into spinning baths containing 16 to 20% sodium sulfate, 4 to 8% zinc sulfate and sulfuric acid not more than about 7.8%, results in the production of all skin filaments. Lesser amounts of sulfuric acid may be employed. Greater amounts of sulfuric acid results in the production of products having skin and core. A lowering of the amount of adduct of aniline, the lowering of the caustic .soda content or the lowering of the salt test of the viscose reduces the maximum permissible acid concentration for the production of all skin filaments. it has been determined'that the maximum concentration of acid which is permissible for the production of all skin products is about 1.35 times the percentage caustic soda content of the viscose and is preferably held between about 1.15 and 1.25 times the percentage caustic soda content of the viscose.

The presence of the adducts of aniline in the viscose retards the coagulation and, therefore, the amount of adduct employed must be reduced at high spinning speeds Thus, for optimum physical characteristics of an all skin yarn formed from a viscose as above and at a spinning speed of about 50 meters per minute, the adduct is employed in amounts Within the lower portion of the range, for example, about 0.5%. The determination of the specific maximum and optimum concentration of acid for any specific viscose, spinning bath and spinning speed is a matter of simple experimentation for those skilled The extruded viscose must, of course, be immersed or maintained in the spinning bath for a period SllfilClCIlt to effect relatively complete coagulation of the viscose, that is, the coagulation must be suificient so that the filaments will not adhere to each other as they are brought together and withdrawn from the bath.

In the production of filaments for such purposes as the fabrication of tire cord, the filaments are preferably stretched after removal from the initial coagulating and regenerating bath. From the initial spinning bath, the filaments may be passed through a hot aqueous bath which may consist of hot water or a dilute acid solution and may be stretched from about 70% to about 120%, preferably between and Yarns for other textile purposes may be stretched as low as 20%. The precise amount of stretching will be dependent upon the desired tenacity and other properties and the specific type of product being produced. It is to be understood that the invention is not restricted to the production of filaments and yarns but it is also applicable to other shaped bodies such as sheets, films, tubes and the like. The filaments may then be passed through a final regenerating bath which may contain from about 1% to about 5% sulfuric acid and from about 1% to about 5% sodium sulfate with or without small amounts of zinc sulfate if regeneration has not previously been completed.

The treatment following the final regenerating bath, or the stretching operation where regeneration has been completed, may consist of a washnig step, a desulfurizing step, the application of a finishing or plasticizing material and drying before or after collecting, or may include other desired and conventional steps such as bleaching and the like. The treatment after regeneration will be dictated by the specific type of shaped body and the proposed use thereof.

Regenerated cellulose filaments prepared from viscose containing the small amounts of the water-soluble alkylene oxide adducts of aniline and spun in the spinning baths of limited acid content have a smooth or noncrenulated surface and consist substantially entirely of skin. Because of the uniformity of structure throughout the filament, the swelling and staining characteristics are uniform throughout the cross-section of the filament.

Filaments producedpursuant to this invention and consisting entirely of skin have a high toughness and a greater flexing life than filaments as produced according to prior inthe production of twisted cords from the filaments' consisting entirely of skin. .Filaments prepared from viscose containing the alkylene oxide adducts of aniline have a high tensile strengtha's compared to normal regenerated cellulose filaments, have superior abrasion and fatigue resistance characteristics and have a high flexlife. Such filaments are highly satisfactory for the production of cords for the reinforcement of rubber products such as pneumatic tire casings, but the filaments are not restricted to such uses and may be used for other textile applications. j

Like improvements in the characteristics and properties of the products are also obtained by incorporating the alkylene oxide adducts of aniline in the spinning bath in place of adding the adduct to the viscose. It is essential that the composition of the spinning bath, particularly the acid concentration be maintained within the limits set forth hereinbefore. In order to produce products consisting of all skin, the amount ofthe alkylene oxide adduct of aniline dissolved. in the spinning bath must be at least about 0.05% .by weight and is preferably maintained at about 0.1%. The upper limit does not appear to be critical as'in the incorporation of the adducts in the viscose. The upper. limit is dependent upon the solubility of the particular adduct and by economic considerations since "amounts exceeding about 0.2% are not more effective in improving the properties of the products.

It is obvious that the adducts may be added to both the viscose and the spinning bath, if desired.v In such instance, it is also essential to maintain the amounts of the adduct of the viscoseand in the spinning bath, and the composition of the spinning bath within the stated limits. The all skin products of improved properties are obtained only when the spinning operation in the presence of the alkylene oxide adducts of aniline is carried out within the spinning bath composition as .set forth hereinbefore.

The invention may be illustrated by reference to the preparation of regenerated cellulose filaments from a viscose containing about 7% cellulose, about 6% caustic soda, and having a total carbon disulfide content of about 41% based on the weight of the cellulose. The viscose solutions were prepared by xanthating alkali cellulose by the introduction of 36% carbon disulfide based on the weight of the cellulose and churning for about 2% hours. The cellulose xanthate was then dissolved in'caustic soda solution. An additional 5% carbon disulfide was then added to the mixer and the mass mixed for about one hour. The viscose was then allowed to ripen for about 30 hours at 18 C. In those instances where the modifier was incorporated in the viscose, the desired amount of an ethylene oxide adduct of aniline was added to the solution and mixed for about /2 hour before allowing the viscose to ripen.

Example 1 Approximately 1% (based on the weight of the cellulose) of an ethylene oxide adduct of aniline containing about 6 ethylene oxide units per molecule of aniline was added to and incorporated in the viscose as described above. The viscose employed in the spinning of filaments had a salt test of 10. The viscose was extruded through a spinneret to form a 1650 denier, 720 filament cord at a rate of about 22 meters per minute. The coagulating and regenerating bath was maintained at a temperature of about 60 and contained 7.1% sulfuric acid, 8%

- 6 zinc sulfate and 17% sodium sulfate. The cord was stretched about washed free of acids and salts by treatment with water at about C. on thread advancing reels, dried and collected on cones.

The individual filaments have a smooth, non-crenulated exterior surface and consist entirely of skin, no core being detectable at high magnification (e.g. 1500 The filaments of a control yarn spun with the same viscose but without the addition of the modified agent and spun under the same conditions, exhibit a very irregular and serrated surface and are composed of about 75% skin and the balance core with. a sharp line of demarkation between the skin and core. Other physical properties are set forth in the table which follows the examples.

Example 2 A viscose solution as described above (no adduct added) having a salt test of 10.7 was spun into a 210 denier, filament yarn by extrusion into a spinning bath containing'7.7% sulfuric acid, 8% zinc sulfate, 17% sodium sulfate and 0.1% of an ethylene oxide adduct of aniline containing about 6 ethylene oxide units per molecule of aniline. The bath was maintained at 60 C. and the extrusion rate was about 22 meters per minute. The filaments were. passed through a hot water bath maintained at about 95 C. and stretched about 82%. The yarn was collected in a spinning box, washed free of acid and salts anddried.

The filaments have a smooth, non-crenulated surface and consist entirely of skin 'while control filaments have a very irregular and serrated surface and consist of about 75 skin and the balance core with a sharp line of demarkation between the skin and core. Other'physical characteristics are set forth in the table which follows the examples.

Example 3 To a viscose as describedabove, there was added 1% of an ethylene oxide adduct of aniline. containing 6 ethylene oxide units per'molecule of aniline. The viscose had a salt test of 10.7 and was spun into a 210 denier, 120 filament yarn by extrusion into a spinning bath containing 7.7% sulfuric acid, 8.3% zinc'sulfate, 17% sodium sulfate, and 0.1%, based on the weight of the cellulose in the viscose, of an ethylene oxide adduct of aniline containing 6 ethylene oxide units per molecule of aniline. The bath .was maintained at 60 C. and the extrusion rate was about 22 meters per minute. The filaments were subsequently passed through a hot water bath at 95 C. and stretched about 82%.- The yarn was collected in a spinning box, washed free of acids and salts and dried.

The individual filaments were readily distinguishable from control filaments in that they have a smooth, noncrenulated surface and consist entirely of skin while the control filaments have a very irregular and serrated surface and consist of about 75 skin and the balance core with a sharp line of demarkation between the skin and the core. Other physical properties are set forth in the table which follows the examples.

Example 4 As a control for the foregoing examples, a viscose solution, prepared as described above, having a salt test of 10 was spun into a 210 denier, 120 filament yarn by extrusion into a bath containing 7.5% sulfuric acid, 8% zinc sulfate and 18% sodium sulfate. The bath was maintained at a temperature of about 60 C. The extrusion rate was about 22 meters per minute. The water bath was maintained at a temperature of about 95 C. and the filaments were stretched 82% while passing through the hot water. The yarn was collected in a spinning box, washed free of acid and salts and dried.

The individual filaments have a very irregular and serrated surface and consist of about 75% skin and the balance core with a sharp line of'demarkation between the skin and the core. Other characteristics are set forth in the table which follows:

Although the tenacity and elongation are the only properties set forth, they have been chosen because of the ease and simplicity with which such properties may be determined. In some instances, products made in accordance ith this invention do not exhibit large or great improvements in tenacity and elongation (Example 3), however, the products consist of a smooth-surfaced, all skin structure and possess improved abrasion resistance, flex-life and other properties as disclosed hereinbefore.

One of the properties of viscose rayon which has limited its uses is its relatively high cross-sectional swelling when Wet with Water, this swelling amounting to from about 65% to about 80% for rayon produced by conventional methods. Rayon filaments produced in accordance with the method of this invention have an appreciably lower cross-sectional swelling characteristic, the swelling amounting to from about 45% to about 60%.

The modifier of this invention may be added to any desired viscose such as those normally used in industry, the specific viscose composition set forth above, being merely for illustrative purposes. The alkylene oxide adduct of aniline may be added at any desired stage in the production of the viscose and may be present in the cellulosic raw material although it may be necessary to adjust the amount present to produce a viscose having the proper proportions of the adduct at the time of spinning.

The term skin is employed to designate that portion of regenerated cellulose filaments which is permanently stained or dyed by the following procedure: A microtome section of one or more of the filaments mounted in a Wax block is taken and'mounted on a slide with Meyers albumin fixative. After dewaxing-in xylene, the section is" placed in successive baths of and 30% alcohol for a few moments each, and it is then stained in 2% aqueous solution of Victoria Blue BS conc. (General Dyestulfs Corp.) for 1 to 2 ho rs. At this point, the entire section is blue. By rinsing the section first in dis tilled water and then in one or more baths composed of 10% water and dioxane for a period varying from 5 to 30' minutes depending on the particular filament, the dye is entirely removed from the core, leaving it restricted to the skin areas.

While preferred embodiments of the invention have been disclosed, the description is intended to be illustrative and it is to be understood that changes and variations may be made without departing from the spirit and scope of the invention as defined by the appended claims.

This application is a division of my copending application entitled Producing All Skin Viscose Rayon, Serial No. 466,677, filed November 3, 1954.

I claim:

1. A viscose spinning. solution containing a small amount of a water-soluble adduct of aniline with ethylene oxide, the adduct containing from about 2 to about 50 ethylene oxide units per molecule of aniline, said small amount of the adduct being a quantity sufficient to impart a smooth, non-crenulated surface and a substantially all skin structure to products formed by spinning the viscose at a salt test of at least 7 into an aqueous bath containing from 10% to 25% sodium sulfate, from 3% to 15% zinc sulfate and sulfuric acid in a percentage not exceeding about 1.25 times the percentage of caustic soda in the viscose, but the quantity being insufficient to adversely affect the physical properties of such products.

2. A viscose spinning solution containing from about 0.2% to about 4%, based on the weight of the cellulose in the viscose, of a water-soluble adduct of aniline with ethylene oxide, the adduct containing from about 2 to about 50 ethylene oxide units per molecule of aniline.

References Cited in the file of this patent UNITED STATES PATENTS 2,125,031 Polak July 26, 1938' 2,373,712 Schlosser et al. Apr. 17, 1945 2,593,466 MacLaurin et a1. Apr. 22, 1952 l l i l l 

1. A VISCOSE SPINNING SOLUTION CONTAINING A SMALL AMOUNT OF A WATER-SOLUBLE ADDUCT OF ANILINE WITH ETHYLENE OXIDE, THE ADDUCT CONTAINING FROM ABOUT 2 TO ABOUT 50 ETHYLENE OXIDE UNITS PER MOLECULE OF ANILINE, SAID SMALL AMOUNT OF THE ADDUCT BEING A QUANTITY SUFFICIENT TO IMPART A SMOOTH, NON-CRENULATED SURFACE AND A SUBSTANTIALLY ALL SKIN STRUCTURE TO PRODUCTS FORMED BY SPINNING THE VISCOSE AT A SALT TEST OF AT LEAST 7 INTO AN AQUEOUS BATH CONTAINING FROM 10% TO 25% SODIUM SULFATE, FROM 3% TO 15% ZINC SULFATE AND SULFURIC ACID IN A PERCENTAGE NOT EXCEEDING ABOUT 1.25 TIMES THE PERCENTAGE OF CAUSTIC SODA IN THE VISCOSE, BUT THE QUANTITY BEING INSUFFICIENT TO ADVERSELY AFFECT THE PHYSICAL PROPERTIES OF SUCH PRODUCTS. 